CN112403519B - Preparation method and application of COF-300/PPy/Au (G) nanoenzyme catalyst - Google Patents
Preparation method and application of COF-300/PPy/Au (G) nanoenzyme catalyst Download PDFInfo
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Abstract
The invention belongs to the technical field of nano material preparation and application, in particular to a preparation method and application of a COF-300/PPy/Au (G) nano enzyme catalyst; firstly, adding terephthalaldehyde and tetra (4-aminophenyl) methane into 1, 4-dioxane, stirring for dissolving, adding acetic acid, standing, and preparing COF-300 by a solvothermal method; then, taking pyrrole monomer as a raw material, taking water as a solvent, and stirring at normal temperature by adopting an in-situ polymerization method to obtain a COF-300@ PPy composite nano material; and finally, preparing the multilayer gold nanoparticle (AuNPs) modified COF-300/PPy/Au (G) nano enzyme catalyst by using chloroauric acid as a raw material and trisodium citrate as a reducing agent through a reduction and in-situ growth method. The COF-300/PPy/Au (G) nano enzyme catalyst prepared by the invention shows high-efficiency broad-spectrum catalytic action, shows strong catalytic degradation removal effect on various organic matters, and has the advantages of mild preparation conditions, simple method, economy and feasibility.
Description
Technical Field
The invention belongs to the technical field of nano material preparation and application, and particularly relates to a preparation method and application of a COF-300/PPy/Au (G) nano enzyme catalyst.
Background
Water is a basic requirement for maintaining life and health, and the phenomenon of water pollution is more and more serious along with the development of social economy. The organic pollutants with the characteristics of heavy chromaticity, high concentration, stable chemical property, complex components, high biological toxicity and the like are discharged into a water body and are difficult to degrade. Therefore, it is important to find a nano material which is environment-friendly, simple in synthesis process, low in price and high in efficiency and can be used for removing pollutants in water. The AuNPs material as a simulated enzyme catalyst has the advantages of higher stability, large-scale acquisition and the like compared with natural enzyme, and is widely applied to the aspect of catalytic degradation and removal of environmental pollutants. However, the simple AuNPs have the risks of easy agglomeration, secondary pollution and the like in water. Therefore, it is also important to find an AuNPs carrier with large specific surface area and easy dispersion.
Covalent Organic Frameworks (COFs) are highly ordered porous, high molecular crystalline materials prepared from small inorganic molecules via covalent bonding. COFs have the characteristics of super-large specific surface area, easy functionalization, low density and the like, and are good catalyst carriers. At present, COFs have certain applications in aspects of gas storage, hydrogen production, organic reaction catalysis and the like. However, the application of the multilayer Au NPs modified COF-300/PPy in the aspect of catalytic degradation of pollutants in water is not reported.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a COF-300/PPy/Au (G) nanoenzyme catalyst, which comprises the following steps:
s1 preparation of COF-300 from benzene dicarbaldehyde, tetrakis (4-aminophenyl) methane, 1, 4-dioxane and acetic acid;
s2, adding pyrrole monomer into COF-300 aqueous solution, and preparing the COF-300@ PPy composite nano material through in-situ polymerization;
s3 preparing a Au NPs solution, and dripping the Au NPs solution into a COF-300/PPy aqueous solution to obtain COF-300/PPy/Au (A);
s4 is used for preparing multilayer Au NPs modified COF-300/PPy/Au (G) nanoenzyme catalysts by a reduction and in-situ growth method.
In S1, the COF-300 is prepared by:
s101, putting terephthalaldehyde and tetra- (4-aminophenyl) -methane into a polytetrafluoroethylene reaction kettle, adding 1, 4-dioxane, and uniformly stirring;
s102, after the mixed solution becomes a transparent bright yellow solution, dropwise adding an acetic acid solution, and standing at room temperature;
s103, placing the mixed solution in a high-pressure reaction kettle to react in an oven at 100 ℃;
the COF-300 prepared by S104 is washed by acetone and dried in vacuum to obtain COF-300 pale yellow powder.
In S2, the specific method for preparing the COF-300@ PPy composite nano material comprises the following steps:
s201, adding COF-300 into ultrapure water to form uniform suspension;
s202, adding pyrrole monomer into the suspension for mixing;
s203 FeCl3·6H2Dropwise adding an O aqueous solution into the mixed solution, stirring, and reacting at normal temperature for 24 hours to obtain a COF-300@ PPy suspension;
s204, alternately washing with ethanol and ultrapure water, and centrifuging to obtain the COF-300@ PPy composite nano material.
The condition for preparing the COF-300@ PPy composite nano material is a light-shielding environment.
In S3, the preparation method of the Au NPs solution is:
s301, adding chloroauric acid and trisodium citrate into ultrapure water, and uniformly mixing;
s302, dropwise adding a sodium borohydride aqueous solution into the mixed solution to prepare an Au NPs solution.
In S3, the preparation method of the COF-300/PPy/Au (A) comprises the following steps:
s303, ultrasonically dispersing COF-300/PPy in ultrapure water to form a mixed solution;
s304, dropwise adding the Au NPs solution into the mixed solution, and stirring at normal temperature to obtain a primary AuNPs modified COF-300/PPy suspension;
s305, alternately washing and drying the suspension by ultrapure water and ethanol to obtain a once AuNPs modified COF-300/PPy solid nano material named as COF-300/PPy/Au (A).
In S4, the preparation method of the COF-300/PPy/Au (G) nanoenzyme catalyst comprises the following steps:
s401, ultrasonically dispersing a COF-300/PPy/Au (A) composite nano material in ultrapure water to form a suspension aqueous solution;
s402, adding chloroauric acid into a COF-300/PPy/Au (A) aqueous solution;
s403, dropwise adding glucose solution into the mixed solution for reaction;
and S404, alternately washing the suspension after the reaction by using ultrapure water and ethanol to obtain the COF-300/PPy/Au (G) nano enzyme catalyst.
The chloroauric acid is added into a COF-300/PPy/Au (A) aqueous solution, and the pH value of the mixed solution is regulated to 10.2 by a NaOH solution.
The invention also aims to provide an application of the COF-300/PPy/Au (G) nanoenzyme catalyst, and particularly relates to an application of the COF-300/PPy/Au (G) nanoenzyme catalyst in degradation of p-nitrophenol (4-NP), Methylene Blue (MB), Congo Red (CR) and Methyl Orange (MO) organic pollutants in water.
The invention has the beneficial effects that: (1) the invention selects COF-300 as a carrier of AuNPs, and by utilizing the multilevel pore structure of COF-300 and the threshold limiting effect of a nanometer pore channel, the growth and agglomeration of AuNPs can be realized, the dispersibility of AuNPs is improved, the specific surface area is increased, the active center of catalytic reaction is increased, and the photocatalytic performance is finally improved. Meanwhile, the COF-300 modified by PPy can immobilize the catalyst, thereby being beneficial to the recovery and the cyclic utilization of the COF-300/PPy/Au (G) nano enzyme catalyst and reducing the secondary pollution.
(2) The invention adopts a solvothermal method, in-situ growth and layer-by-layer self-assembly methods to prepare the COF-300/PPy/Au (G) nano enzyme catalyst. The in-situ growth prepared single-layer AuNPs modified COF-300/PPy/Au (A) nano material has the AuNPs content of 2-6% by mass. And the AuNPs of the multilayer AuNPs modified COF-300/PPy/Au (G) nanoenzyme catalyst prepared by in-situ growth and layer-by-layer self-assembly have the mass content of 20-28%. And 4-NP, MB, CR and MO are used as simulated pollutants to evaluate the catalytic degradation performance of the prepared material. The influence of the catalytic time and the composite nano-enzyme catalyst with different Au NPs carriers on the catalytic degradation performance of pollutants is investigated. The results show that the catalytic performance of the COF-300/PPy/Au (G) nanoenzyme catalyst is obviously higher than that of the COF-300/PPy/Au (A).
(3) The COF-300/PPy/Au (G) nano enzyme catalyst prepared by the invention shows better stability, and the degradation effect on 4-NP is not obviously changed after the catalyst is placed at room temperature for 5 weeks.
Drawings
FIG. 1 is a synthetic route of COF-300/PPy/Au (G) complex nanoenzyme catalyst;
FIG. 2 is an IR spectrum of COF-300, COF-300/PPy and COF-300/PPy/Au (G);
FIG. 3 is a scanning electron micrograph of COF-300, COF-300/PPy/Au (A), and COF-300/PPy/Au (G);
FIG. 4 is a graph of the removal rate of 4-NP degradation by COF-300/PPy/Au (A) and COF-300/PPy/Au (G) nanoenzyme catalysts over time;
FIG. 5 is a graph showing the degradation removal rate of the COF-300/PPy/Au (A) and the COF-300/PPy/Au (G) nanoenzyme catalysts for MB with time;
FIG. 6 is a graph showing the removal rate of the COF-300/PPy/Au (A) and COF-300/PPy/Au (G) nanoenzyme catalysts against the degradation of CR with time;
FIG. 7 is a graph of the rate of removal of MO degradation by COF-300/PPy/Au (A) and COF-300/PPy/Au (G) nanoenzyme catalysts over time;
FIG. 8 shows the catalytic degradation removal rate of COF-300@ PPy @ Au (G) nanoenzyme catalyst on 4-NP in five weeks.
Detailed Description
The technical scheme of the invention is further explained by specific embodiments in the following with the accompanying drawings:
the preparation method and application of the COF-300/PPy/Au (G) nanoenzyme catalyst of the invention are described in detail by specific examples below.
The COF-300/PPy/Au (G) nano enzyme catalyst is prepared by adopting a solvothermal method, in-situ growth and a layer-by-layer self-assembly method, and is shown in figure 1.
The first step is to prepare the COF-300 nano material by taking terephthalaldehyde and tetra- (4-aminophenyl) -methane as raw materials and using a solvothermal method. And in the second step, modifying the COF-300 with PPy by using an in-situ polymerization method to prepare the COF-300/PPy nano material. The third step is to prepare COF-300/PPy/Au (A) and COF-300/PPy/Au (G) nano enzyme catalysts by using in-situ growth and layer-by-layer self-assembly methods and taking gold chlorate and COF-300/PPy as raw materials.
Example 1
The preparation method of the COF-300/PPy/Au (G) nanoenzyme catalyst comprises the following steps:
preparation of COF-300
Accurately weighing 12mg of terephthalaldehyde and 20mg of tetra- (4-aminophenyl) -methane, putting the terephthalaldehyde and the methane into a 10mL polytetrafluoroethylene reaction kettle, adding 1mL of 1, 4-dioxane, stirring uniformly by using a glass rod until the mixture becomes a transparent bright yellow solution, dropwise adding 0.2mL of 3M acetic acid solution, and standing at room temperature for 2-5 hours; putting the mixed solution into a 10mL high-pressure reaction kettle, and reacting for 72h at 100 ℃; naturally cooling to room temperature, repeatedly washing with acetone for many times, and vacuum drying at 60 deg.C for 2-6h to obtain COF-300 pale yellow powder.
Preparation of COF-300/PPy
Under the condition of keeping out of the sun, weighing 200mg of COF-300, adding into 20mL of ultrapure water, performing ultrasonic treatment for 1-2h, and uniformly dispersing; then 0.8mL pyrrole monomer was added to the above suspension and after magnetic stirring at 1500rpm for 2h, 4mL of 0.185M FeCl was added3Dropwise adding the 6H2O aqueous solution into the mixed solution, and magnetically stirring for 24 hours; washing with ethanol and ultrapure water alternately for multiple times, and then drying in a vacuum drying oven at 60 ℃ for 4-6h to obtain the COF-300/PPy nano material.
Preparation of COF-300/PPy/Au (G) composite nanoenzyme catalyst
Adding 18.5mL of ultrapure water into 0.01M chloroauric acid aqueous solution of 0.5mL and trisodium citrate aqueous solution of 0.01M of 0.5mL, stirring for 5min by magnetic force, dropwise adding 0.5mL of 0.1M sodium borohydride solution, and changing the solution into orange, namely the prepared Au NPs solution (marked as solution A); ultrasonically dispersing 30mg of COF-300/PPy in 20mL of ultrapure water, then dropwise adding the solution A into a COF-300/PPy aqueous solution, magnetically stirring for 1-3h, alternately washing with the ultrapure water and ethanol for multiple times, and drying in vacuum at 60 ℃ for 4-6h to obtain once Au NPs modified COF-300/PPy, which is named as COF-300/PPy/Au (A); accurately weighing 30mg of COF-300/PPy/Au (A) composite nano material, ultrasonically dispersing the COF-300/PPy/Au (A) composite nano material in 20mL of ultrapure water, adding 26mL of 2.2mM chloroauric acid aqueous solution into the COF-300/PPy/Au (A) aqueous solution, and adjusting the pH value of the mixed solution to 10.2 by using 0.1M NaOH solution; then 9mL of 0.1M aqueous glucose solution was added dropwise to the solution, stirred for 9-12h, and the resulting material was washed with ultrapure water and ethanol alternately several times to obtain a multilayer Au NPs-modified COF-300/PPy/Au (G) nanoenzyme catalyst.
FIG. 2 is an infrared spectrogram of COF-300, COF-300/PPy and COF-300/PPy/Au (G), and the infrared characterization proves that the COF-300/PPy/Au (G) composite nanoenzyme catalyst is successfully prepared.
FIG. 3 is a Scanning Electron Micrograph (SEM) of COF-300, COF-300/PPy/Au (A), and COF-300/PPy/Au (G). As can be seen from the figure, the prepared COF-300 is a crystalline material with a rice-like granule structure, and PPy and Au NPs are successfully modified on the surface of the COF-300 nano material.
After the content of Au NPs in the prepared COF-300/PPy/Au (A) and COF-300/PPy/Au (G) nanoenzyme catalysts is determined by ICP-AES, the content of the Au NPs in the COF-300/PPy/Au (A) composite nanomaterial modified by the single-layer Au NPs is 2-6% by mass. And the mass content of the Au NPs of the COF-300/PPy/Au (G) nano enzyme catalyst modified by the multilayer Au NPs prepared by in-situ growth and layer-by-layer self-assembly is 20-28%.
Catalytic degradation of 4-NP
To a 1cm quartz cuvette were added 2.75mL of ultrapure water, 30. mu.L of a 10.0M solution of 4-NP, and 200. mu.L of 0.1M NaBH4The aqueous solution is subjected to ultrasonic treatment for 20s to uniformly disperse the aqueous solution. Next, 20. mu.L of 1.0mg/mL COF-300@ PPy @ Au (G) (or COF-300@ PPy @ Au (A)) nanoenzyme catalyst was added to the above solution, and the reaction was started by stirring for 10 seconds. The change in absorbance at a wavelength range of 396nm was detected using UV-Vis. Using the standard curve, the concentration C of 4-NP in the solution was obtained, and the initial concentration of 4-NP was assumed to be C0According to the formula: (1-C/C0) 100%, the degradation efficiency (R) of 4-NP was calculated.
The influence of COF-300@ PPy @ Au (A) and COF-300@ PPy @ Au (G) nanoenzyme catalysts on the catalytic effect of 4-NP in different catalytic reaction times is explored, and is shown in FIG. 4. As can be seen from FIG. 4, when the catalytic time is 21min, the degradation efficiency of the COF-300@ PPy @ Au (G) nano enzyme catalyst on 4-NP reaches 99.71 percent, which is obviously higher than that of the COF-300@ PPy @ Au (A) composite nano material. The multilayer Au NPs modified COF-300@ PPy @ Au (G) nanoenzyme catalyst has better catalytic activity and degradation efficiency, and the highly toxic 4-NP can be converted into the less toxic 4-AP in a shorter time.
MB experiment for catalytic degradation
2.5ml of 6.25mg/L MB, 480. mu.L of 0.1M NaBH were added to a 1cm quartz cuvette4Dissolving in waterLiquid ultrasound is carried out for 20s to ensure that the mixture is dispersed uniformly. Next, 20. mu.L of 1.0mg/mL COF-300@ PPy @ Au (G) (or COF-300@ PPy @ Au (A)) nanoenzyme catalyst was added to the above solution, and the reaction was started by stirring for 10 seconds. The change in absorbance at the wavelength range of 660nm was detected using UV-Vis. The MB solution concentration C was obtained using a standard curve, and the initial concentration of MB was set as C0According to the formula: (1-C/C0) 100%, the degradation efficiency (R) of MB was calculated.
The influence of COF-300@ PPy @ Au (A) and COF-300@ PPy @ Au (G) nanocatalysis enzymes on the catalytic effect of the MB in different catalytic reaction times is explored, and is shown in FIG. 5. From FIG. 5, it can be seen that when the catalytic time is 12min, the degradation efficiency of the COF-300@ PPy @ Au (G) nano enzyme catalyst on MB reaches 94.27%, which is obviously higher than that of the COF-300@ PPy @ Au (A) composite nano material. The multilayer Au NPs modified COF-300@ PPy @ Au (G) nanoenzyme catalyst has better catalytic activity and degradation efficiency.
Catalytic degradation CR experiment
2.5ml of 6.25mg/L CR, 480. mu.L of 0.1M NaBH were added to a 1cm quartz cuvette4The aqueous solution is dispersed uniformly by ultrasonic treatment for 20 s. Next, 20. mu.L of 1.0mg/mL COF-300@ PPy @ Au (G) (or COF-300@ PPy @ Au (A)) nanoenzyme catalyst was added to the above solution, and the reaction was started by stirring for 10 seconds. The change in absorbance at the 497nm wavelength range was detected using UV-Vis. Using a standard curve, the concentration C of the CR solution was obtained, and the initial concentration of CR was set as C0According to the formula: (1-C/C0) 100%, the degradation efficiency (R) of CR was calculated.
The influence of COF-300@ PPy @ Au (A) and COF-300@ PPy @ Au (G) nanocatalysts on the catalytic effect of CR in different catalytic reaction times is explored, and is shown in FIG. 6. As can be seen from FIG. 6, when the catalytic time is 10min, the degradation efficiency of the COF-300@ PPy @ Au (G) nano-enzyme catalyst on CR reaches 94.68%, which is obviously higher than that of the COF-300@ PPy @ Au (A) composite nano-material. The multilayer Au NPs modified COF-300@ PPy @ Au (G) nanoenzyme catalyst has better catalytic activity and degradation efficiency.
MO experiment of catalytic degradation
2.5mL of 12.25mg/L CR, 480. mu.L of 0.1MNaBH were added to a 1cm quartz cuvette4Aqueous solution superThe sound 20s makes it disperse uniformly. Next, 20. mu.L of 1.0mg/mL COF-300@ PPy @ Au (G) (or COF-300@ PPy @ Au (A)) nanoenzyme catalyst was added to the above solution, and the reaction was started by stirring for 10 seconds. The change in absorbance at the 462nm wavelength range was detected using UV-Vis. Using a standard curve to obtain the concentration C of the MO solution, and setting the initial concentration of MO as C0According to the formula: (1-C/C0) 100%, the degradation efficiency (R) of MO was calculated.
The influence of COF-300@ PPy @ Au (A) and COF-300@ PPy @ Au (G) nanocatalysts on the MO catalytic effect in different catalytic reaction times is explored, and is shown in FIG. 7. From FIG. 7, it can be seen that when the catalytic time is 7min, the degradation efficiency of the COF-300@ PPy @ Au (G) nano-enzyme catalyst on MO reaches 97.72%, which is obviously higher than that of the COF-300@ PPy @ Au (A) composite nano-material. The multilayer Au NPs modified COF-300@ PPy @ Au (G) nanoenzyme catalyst has better catalytic activity and degradation efficiency.
The stability of COF-300@ PPy @ Au (G) nanocatalyst was examined over five weeks. The catalytic degradation effect of the COF-300@ PPy @ Au (G) composite nano catalytic enzyme on 4-NP in five weeks is researched. As can be seen from FIG. 8, the catalytic degradation efficiency of the COF-300@ PPy @ Au (G) composite nanocatalyst enzyme on 4-NP can still reach about 95% within five weeks. Therefore, the COF-300@ PPy @ Au (G) composite nano catalytic enzyme has better stability, can be stored for a long time and does not influence the catalytic activity of the nano catalytic enzyme
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. A preparation method of COF-300/PPy/Au (G) nanoenzyme catalyst is characterized in that: comprises that
S1 preparation of COF-300 from benzene dicarbaldehyde, tetrakis (4-aminophenyl) methane, 1, 4-dioxane and acetic acid;
s2, adding pyrrole monomer into COF-300 aqueous solution, and preparing the COF-300@ PPy composite nano material through in-situ polymerization;
s3, preparing AuNPs solution, and dripping the AuNPs solution into COF-300/PPy aqueous solution to obtain COF-300/PPy/Au (A);
s4 multilayer AuNPs modified COF-300/PPy/Au (G) nanoenzyme catalyst is prepared by the following steps:
s401, ultrasonically dispersing a COF-300/PPy/Au (A) composite nano material in ultrapure water to form a suspension aqueous solution;
s402, adding chloroauric acid into a COF-300/PPy/Au (A) aqueous solution;
s403, reacting glucose solution added dropwise into the suspended water solution;
and S404, alternately washing the suspension after the reaction by using ultrapure water and ethanol to obtain the COF-300/PPy/Au (G) nano enzyme catalyst.
2. The method for preparing a COF-300/PPy/Au (G) nanoenzyme catalyst according to claim 1, wherein the method comprises the following steps: in S1, the COF-300 is prepared by:
s101, putting terephthalaldehyde and tetra- (4-aminophenyl) -methane into a polytetrafluoroethylene reaction kettle, adding 1, 4-dioxane, and uniformly stirring;
s102, after the mixed solution becomes a transparent bright yellow solution, dropwise adding an acetic acid solution, and standing at room temperature;
s103, placing the mixed solution in a high-pressure reaction kettle to react in an oven at 100 ℃;
s104 reaction to obtain COF-300, washing the COF-300 by acetone, and drying the COF-300 in vacuum to obtain light yellow powder of the COF-300.
3. The method for preparing a COF-300/PPy/Au (G) nanoenzyme catalyst according to claim 1, wherein the method comprises the following steps: in S2, the specific method for preparing the COF-300@ PPy composite nano material comprises the following steps:
s201, adding COF-300 into ultrapure water to form uniform suspension;
s202, adding pyrrole monomer into the suspension for mixing;
s203 FeCl3·6H2Dropwise adding an O aqueous solution into the mixed solution, stirring, and reacting at normal temperature for 24 hours to obtain a COF-300@ PPy suspension;
s204, alternately washing with ethanol and ultrapure water, and centrifuging to obtain the COF-300@ PPy composite nano material.
4. The method for preparing COF-300/PPy/Au (G) nanoenzyme catalyst according to claim 3, wherein: the condition for preparing the COF-300@ PPy composite nano material is a light-shielding environment.
5. The method for preparing a COF-300/PPy/Au (G) nanoenzyme catalyst according to claim 1, wherein the method comprises the following steps: in S3, the method for preparing the AuNPs solution is as follows:
s301, adding chloroauric acid and trisodium citrate into ultrapure water, and uniformly mixing;
s302, adding a sodium borohydride aqueous solution into the mixed solution drop by drop to prepare the AuNPs solution.
6. The method for preparing a COF-300/PPy/Au (G) nanoenzyme catalyst according to claim 1, wherein the method comprises the following steps: in S3, the preparation method of the COF-300/PPy/Au (A) is that
S303, ultrasonically dispersing COF-300/PPy in ultrapure water to form a mixed solution;
s304, adding the AuNPs solution into the mixed solution drop by drop;
s305, alternately washing and drying the suspension by ultrapure water and ethanol to obtain a once AuNPs modified COF-300/PPy solid nano material named as COF-300/PPy/Au (A).
7. The method for preparing a COF-300/PPy/Au (G) nanoenzyme catalyst according to claim 1, wherein the method comprises the following steps: the chloroauric acid is added into a COF-300/PPy/Au (A) aqueous solution, and the pH value of the mixed solution is regulated to 10.2 by a NaOH solution.
8. Use of a COF-300/PPy/au (g) nanoenzyme catalyst prepared by the method of claim 1, wherein the method comprises the steps of: application of COF-300/PPy/Au (G) nanoenzyme catalyst in degradation of p-nitrophenol, methylene blue, Congo red and methyl orange organic pollutants in water.
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